CN1007353B - Polymerization of olefins using a ziegler-natta catalyst and two organometallic compounds - Google Patents
Polymerization of olefins using a ziegler-natta catalyst and two organometallic compoundsInfo
- Publication number
- CN1007353B CN1007353B CN86105978A CN86105978A CN1007353B CN 1007353 B CN1007353 B CN 1007353B CN 86105978 A CN86105978 A CN 86105978A CN 86105978 A CN86105978 A CN 86105978A CN 1007353 B CN1007353 B CN 1007353B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- organometallic compound
- amount
- alpha
- catalyzer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000002902 organometallic compounds Chemical class 0.000 title claims abstract description 49
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 29
- 239000011954 Ziegler–Natta catalyst Substances 0.000 title abstract description 5
- 150000001336 alkenes Chemical class 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000004711 α-olefin Substances 0.000 claims abstract description 33
- 150000003624 transition metals Chemical class 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 12
- 239000011777 magnesium Substances 0.000 claims abstract description 11
- 230000000737 periodic effect Effects 0.000 claims abstract description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract 3
- 239000003426 co-catalyst Substances 0.000 claims description 28
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 230000008676 import Effects 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 239000004411 aluminium Substances 0.000 claims description 14
- 150000002899 organoaluminium compounds Chemical class 0.000 claims description 14
- 238000012725 vapour phase polymerization Methods 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 150000003752 zinc compounds Chemical class 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 3
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims description 3
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 claims description 3
- 125000002524 organometallic group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000003863 metallic catalyst Substances 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 4
- 238000012685 gas phase polymerization Methods 0.000 abstract description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 29
- 239000010936 titanium Substances 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000000843 powder Substances 0.000 description 23
- 229920001577 copolymer Polymers 0.000 description 20
- 229910052719 titanium Inorganic materials 0.000 description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 18
- 238000007334 copolymerization reaction Methods 0.000 description 17
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 16
- 239000007789 gas Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 150000002431 hydrogen Chemical class 0.000 description 11
- 239000012495 reaction gas Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 238000005243 fluidization Methods 0.000 description 10
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 229910001629 magnesium chloride Inorganic materials 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 150000002736 metal compounds Chemical class 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 7
- 230000005526 G1 to G0 transition Effects 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- -1 halide derivative of titanium Chemical class 0.000 description 7
- 229920000098 polyolefin Polymers 0.000 description 7
- 150000003609 titanium compounds Chemical class 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 150000002681 magnesium compounds Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000003134 recirculating effect Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 150000002901 organomagnesium compounds Chemical class 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002195 fatty ethers Chemical class 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000001141 propulsive effect Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/904—Monomer polymerized in presence of transition metal containing catalyst at least part of which is supported on a polymer, e.g. prepolymerized catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a process for the gas-phase polymerization of alpha-olefins in the presence of a Ziegler-Natta catalyst system comprising a catalyst containing halogen, magnesium and a transition metal, and a cocatalyst containing an organometallic compound of a metal of group II or III of the periodic Table of the elements. The catalyst system is first converted into a prepolymer or catalyst support particles. The process is characterized in that one or more alpha-olefins are brought into contact, on the one hand, with a prepolymer or supported catalyst containing a small amount of volatile organometallic compound as catalyst and, on the other hand, with a cocatalyst containing a volatile organometallic compound (b) to carry out the polymerization in the gas phase, the total amount of cocatalyst used being relatively small.
Description
The present invention relates to alpha-olefin under low pressure adopts the Ziegler-Natta catalyst system to carry out vapour phase polymerization or copolymerization to produce polyolefinic method.
Learn, a kind of catalyst system that is called the olefinic polymerization and the copolymerization of Z-N system, on the one hand, as catalyzer, it is made up of the transistion metal compound of periodic table of elements IV, V or VI family, as co-catalyst, it is made up of the organometallic compound of periodictable II, III family metal on the other hand.What this catalyzer was the most frequently used is the halide derivative of titanium and vanadium, preferably has magnesium compound, and in addition, what this co-catalyst was the most frequently used is organoaluminum or organic zinc compound.
The polymerization of alpha-olefin in gas phase is known.For example adopt to improve and comprise that the air-flow that will carry out the polymeric alpha-olefin remains on formed during the course solid polymer and is in flow state in the fluidized-bed.Reaction gas mixture recirculation after leaving reactor enters reactor and will cool off as last.The amount of replenishing alpha-olefin according to the amount that is consumed.Fluidizing velocity should be able to satisfy the homogeneity of fluidized-bed and the cooling performance of reaction bed well.Polymerization can adopt the catalyzer of Ziegler-Natta type to finish.It can be continuous or semi-continuous adding fluidized-bed reactor.Derive polymer product, similarly also can adopt continuously or semicontinuous method.
Know that former used catalyst system can change prepolymer into during as the catalyzer of vapour phase polymerization, this is called in operation and obtains in " prepolymerization effect ".The prepolymerization effect is comprising that used catalyzer and co-catalyst contact with the alpha-olefin of one or more.Catalyst system changes the condition that prepolymer must be suitable for vapour phase polymerization into, particularly about the size of prepolymer particle and its catalytic activity.
Gas phase polymerization process can be used for making the polyolefine (the per unit weight catalyzer per hour produces the weight of polymkeric substance) of high yield.The polyolefine of industrialization manufacturing contains that the residual catalyst of minute quantity and it can be changed product into again and the step that need not to carry out any separating catalyst.Here it is adopts the advantage of high activity catalyst system.Even 'alpha '-olefin monomers is when being in low relatively dividing potential drop, adopt high activity catalytic system also might in gas phase, obtain quite high percent polymerization.This highly active catalyst system like this, depressing at quite low branch can polymerization of Alpha-olefin, and this just can be used for preventing or the monomer condensation effect takes place when vapour phase polymerization or copolymerization for the alpha-olefin that reduces easy condensation.
The activity of having known certain Z-type catalyst system can adopt increase as the amount of the organometallic compound of co-catalyst and improve.In the case, generally be in polymerisation medium, to be necessary to use quite a large amount of organometallic compounds, yet this is very disadvantageous, includes safety problem as co-catalyst, promptly contact the problem that produces spontaneous combustion with air about these organometallic compounds.
In addition, the polymerization process of alpha-olefin normally uses chain-transfer agent in the mixture of reactant gases in gas phase, and hydrogen for example reduces the molecular-weight average of polyolefin product.Have been found that and adopt hydrogen and adopt a large amount of organometallic compounds will impel the hydrogenation of alpha-olefin simultaneously and form alkane, thereby damaged polyreaction.When using the inert catalyst system, the alkane of this formation is accumulated in the reaction gas mixtures and has reduced output in this polymerization process.
A large amount of technical advice co-catalysts have been arranged, for example, directly co-catalyst is joined in the polymerization reactor and go, or catalyzer and co-catalyst contacted before adding polymerisation medium, yet, at latter event, be actually when polymerization begins employed catalyzer and have maximum activity.Thereby this just might be difficult to prevent to react uncontrollable and form hot spot and made the polymer melt gel.
This equally also might as described abovely combine two kinds of technology that adopt co-catalyst, and the amount that employing adds the co-catalyst increase of polymerization reactor surpasses earlier and the contacted amount of catalyzer.Yet, observe, howsoever, under these conditions, in this polymerisation medium, be necessary to use quite a large amount of co-catalysts, thereby caused above-mentioned shortcoming, such amount total metal content in its catalyzer is between 10 to 500 to the atomic ratio of transition metal consumption in catalyzer, normally between 20 to 100.
The present invention is particularly about using Ziegler-natta catalyst system, the method for polymerization of Alpha-olefin in gas phase.This catalyst system comprise the catalyzer that exists with the prepolymer form with by a certain amount of co-catalyst that includes two kinds of different organometallic compounds in the polymerization process at least that adds respectively.Be surprised to find that and adopt present method might improve polyolefinic productive rate and in reactor, can not form hot spot or melt gel, and can reduce the hydrogenation that alkene changes alkane into simultaneously.Adopt the polyolefine that this method can prepare suitable low residue catalyzer.
The method of olefinic polymerization provided by the present invention, the step that comprises is: (A) a kind of prepolymer of preparation is catalyst based, its preparation process is that one or more alpha-olefins are contacted with the catalyst system of Ziegler-Natta type, this system is that a kind of having consisted essentially of in the halogen magnesium atom and the periodic table of elements belongs to IV on the one hand, the catalyzer of the transition metal atoms of V or VI family, on the other hand, it is a kind of co-catalyst of one or more organometallic compounds that belong to II in the periodic table of elements or III family and (B) prepolymer is catalyst based to contact with one or more alpha-olefins making in the presence of the organo-metallic co-catalyst and under the condition in vapour phase polymerization.The method is characterized in that:
(1) employed co-catalyst is a kind of organometallic compound (a) of low volatility at least in step (A), its vapour pressure in the time of 80 ℃ less than 65 handkerchiefs, the amount of metal is at least 0.5 and mostly be 2.5 most with the atomic ratio of the amount of transition metal in catalyzer in organometallic compound (a), be at least preferably 0.8 and mostly be most 2 and
(2) employed co-catalyst is a kind of volatility organic metal compound (b) at least in step (B), its vapour pressure is equal to or greater than 65Pa in the time of 80 ℃, in organometallic compound (b) amount of metal to the atomic ratio with transition metal consumption in prepolymer is catalyst based be at least 0.5 and at organometallic compound (a) and the total metal content (b) be 2.5 at least and be at most 9 with the atomic ratio of transition metal consumption in catalyzer, be 3 preferably at least and be at most 7.Organometallic compound (b) is to go with catalyst based the importing in the polymerisation medium respectively of prepolymer.
Employed in the method for the invention organometallic compound (a) preferably comprises at least a low volatility organometallic compound, and its general formula is:
AlRnX
3-n
Wherein R representative comprises the alkyl of from 4 to 20 carbon atoms, and X is that hydrogen or halogen atom or alcoholate base and n are any integer or the marks from 1-3.This organometallic compound (a) can be selected from one or more three-n-butylaluminum, three-n-hexyl aluminium, three-octyl aluminum, diisobutyl alanate and diisobutyl aluminum muriate especially, reaction between trialkylaluminium or alkyl aluminum hydride and the isoprene and the aggretion type organo-aluminium compound that makes, (for example the compound of " isoprene aluminium " by name is known) also is suitable.
The vapour pressure of organometallic compound (a) less than 65Pa, better is less than 40 handkerchiefs in the time of 80 ℃.
Employed in the method for the invention organometallic compound (b) preferably comprises one or more organo-aluminium compounds, and its general formula is:
AlR′nX
3-n
Wherein R ' representative comprises the alkyl of from 1 to 3 carbon atom, and X is that hydrogen or halogen atom or alcoholate base and n are from 1 to 3 any integer or marks.Can select wherein one or more three-aluminium triethyl, three-n-propyl aluminium especially for use, diethyl aluminum muriate and ethyl aluminium sesqui chloride.Equally also can select for use one or more volatility organic zinc compounds such as zinc ethyl as organometallic compound (b).
The vapour pressure of organometallic compound (b) is higher than 100Pa in the time of 80 ℃ preferably, preferably at 100-2, in the scope of 000 handkerchief.
Organometallic compound (b) imports polymerization reactor preferably in catalyst based with prepolymer (to call prepolymer in the following text) different inlet point, preferably in the distant inlet point of distance.Also can go according to continuous or semi-continuous it is imported in the polymerisation medium of various known methods.For example, can import or in one or more liquid alpha-olefins, import, perhaps in the hold-up aliphatic hydrocarbon that includes 4 to 6 carbon atoms, import as solution with liquid state as solution.
According to catalyzer of the present invention, the general formula that preferably has:
Wherein Me is aluminium atom and/or zinc atom, and M is the transition metal atoms that belongs to IV in the periodic table of elements, V or VI family, better is titanium and/or vanadium atom, R
1Be the alkyl that includes 2 to 14 carbon atoms, R
2Be the alkyl that includes 2 to 12 carbon atoms, X be chlorine and or bromine atoms, D comprises at least one oxygen or sulphur, or nitrogen, or the electron-giving body compound of phosphorus atom.
Wherein m comprises between 0.5 and 50, better is the number that comprises between 1 and 10, and n comprises between 0 and 1, better is the number that comprises between 0 and 0.5.P is the number that comprises between 0 and 3, and q comprises between 0 and 1, better is the number that comprises between 0 and 0.5, and r comprises between 2 and 104, better is the number that comprises between 3 and 24, and s comprises between 0 and 60, better is the number that comprises between 0 and 20.
Catalyzer can adopt the whole bag of tricks and make, for example, some of them are magnesium compounds, as magnesium chloride, be based upon on the basis that has a kind of transistion metal compound existence at least, perhaps some of them are that magnesium compound and one or more transistion metal compounds are simultaneously precipitated.
For example, catalyzer can be reacted with its highest valency and made by organo-magnesium compound and titanium compound, can select the electron donor Compound D arbitrarily for use, for example selects for use arbitrarily from amine, amides, phosphorus hydrogen type, sulfoxide class and fatty ethers.
Preferably catalyzer reacts between-20 ℃ to 150 ℃ and makes, and is one or more tetravalent titanium compounds, and its general formula is:
Wherein X is the chlorine or bromine atom, R
1Be that alkyl and the t that contains from 2 to 14 carbon atoms comprises integer or the mark 0 to 3 and have general formula to be R
2MgX or general formula are Mg(R
2)
2Organo-magnesium compound, wherein X is oxygen or bromine atoms and R
2It is the alkyl that comprises from 2 to 12 carbon atoms.Reaction between tetravalent titanium compound or titanium compound and organo-magnesium compound is as general formula R
2It is very favourable that the alkyl halide of X exists down, wherein R
2Have above-mentioned identical definition with X, can select the electron-giving body Compound D arbitrarily for use simultaneously.
The technology of another kind of preparation catalyzer is that the magnesium metal reacts with alkyl halide and one or more tetravalent titanium compounds between-20 and 150 ℃.The general formula of these compounds of the latter is R
2X and TiX
4-t(OR
1) t, wherein with top identical and select electron-giving body thing D arbitrarily for use, in the case, the mole ratio of reactant is as follows respectively in the definition of symbol:
TiX
4-t(OR
1) t/Mg is included between 0.05 and 0.5, and better is to be included between 0.1 and 0.33.
R
2X/Mg is included between 0.5 and 8, and better is to be included between 1.5 and 5.
D/TiX
4-t(OR
1) t is included between 0 and 0.5, and better is to be included between 0 to 0.2.
The method that catalyzer also can adopt transistion metal compound to be deposited to basically on the solids of being made up of magnesium chloride prepares.
The magnesium chloride solids particle for example can be reacted by following condition and made by organo-magnesium compound and chlorinated organic cpd:
-organo-magnesium compound or general formula are R
3MgR
4Dialkyl magnesium, or general formula is R
3MgR
4, XAl(R
5)
3The organic-magnesium derivative, R wherein
3, R
4And R
5Be that identical or different alkyl with 2 to 12 carbon atoms and X are included in 0.01 and 1 numerical value.
-chlorinated organic cpd is meant that general formula is R
6The kelene of Cl, wherein R
6Be to have the secondary of 3 to 12 carbon atoms or tertiary alkyl preferably.
-reaction is carried out having in the presence of the electron-giving body Compound D.Compound D is to be selected from amine, phosphorus hydrogen type, sulfoxide class, sulfone class or fatty ethers.
The precipitating action of transistion metal compound on solid magnesium chloride grain can be used the transistion metal compound as titanium or vanadium, carries out reduction reaction and makes with the organometallic compound of its highest valency and periodic table of elements II and III family.Preferably adopt and be: TiX as general formula
4-t(OR
1) titanium compound of t, wherein R
1, X and t are as above-mentioned definition.Reduction reaction can adopt and be selected from general formula is R
3MgR
4Organo-magnesium compound, R wherein
3And R
4Has a same definition with above-mentioned.General formula is Zn(R
7)
2The organic zinc compound of-yXy, wherein R
7Be the alkyl with from 2 to 12 carbon atoms, X is that chlorine or bromine atom and y are zero or 1, or the mark between 0 and 1.General formula Al(R
8)
3The organo-aluminium compound of zXz, wherein R
8Be the alkyl with from 2 to 12 carbon atoms, X is that chlorine or bromine atom and Z are zero.1 or 2, or the fractional reductive agent between 0 and 2 is finished.
Preferably adopt the organometallic compound of q.s in reduction reaction, (for example organic-magnesium, organic zinc or organo-aluminium compound) reduces titanium compound becomes at a low price state.If it is excessive that this kind organic compound uses, preferably before carrying out prepolymerisation stage, from catalyzer, separate.
Described reduction reaction can be selected for use arbitrarily under the existence of above-mentioned electron-giving body Compound D, and temperature is included between-30 ℃ and 100 ℃, and reacts in the liquid hydrocarbon medium.In order to want polypropylene or to want propylene copolymerization and ethene or other alpha-olefins, catalyst system therefor not only will satisfy the polymeric activity, and high stereospecific degree also will be arranged.In this case, a kind of method preferably of preparation catalyzer is arranged, comprise the solids that flood magnesium chloride with tetracol phenixin, for example prepared as stated above such, this dipping preferably carries out in the presence of the electron-giving body Compound D.
Employing comprises that the method for following two steps can be prepared this catalyzer easily:
(a) adopt the electron-giving body Compound D of a kind of ester that especially is selected from aromatic acid or aromatic oxide to handle the solids of magnesium chloride.
(b) adopt titanium tetrachloride to flood the magnesium chloride solids particle of this processing.
Adopting the amount of electron-giving body Compound D, when the 1st step, generally is each mole magnesium compound, comprises that treatment temp can be included as between 20 ℃ and 50 ℃ with the electron-giving body compound between 0.06 and 0.2 mole.When the 2nd one-step chlorination magnesium solids adopt the titanium tetrachloride dipping, can be with pure or in the liquid hydrocarbon medium, carry out.A kind of method particularly is included in titanium tetrachloride and has the solids that grind magnesium chloride down.The amount of titanium tetrachloride should satisfy the consumption requirement that can be fixed on these particles, promptly is per 100 grammeatom magnesium with 0.5 to 3 grammeatom titanium, and dipping temperature comprises greatly between 80 ℃ and 150 ℃.
When one of according to the method described above preparing catalyzer, the solids that generally obtain, its granularity generally is less than 50 microns with when directly being used in the polymerization of carrying out alkene in the gas fluidized bed, generally can not satisfy polymerization activity.
In order to overcome this problem, change catalyzer into prepolymer.
Changing prepolymer into contains and the contacted catalyzer of one or more alpha-olefins, at least adopt a kind of organometallic compound (a) as co-catalyst, its consumption is, the amount of metal is at least 0.5 and be at most 2.5 with the atom ratio of the amount of transition metal in catalyzer in organometallic compound (a), preferably is at least 0.8 and be at most 2.Yet a part that is used organometallic compound (a) amount can be added in the prepolymer and go when changing end.The prepolymerization effect can or in being suspended in liquid medium, as be suspended in fat hydrocarbon or the liquid alpha-olefines, perhaps in gas phase, carry out.When every gram prepolymer contains 2 * 10
-3To 10
-1, better be 4 * 10
-3To 3 * 10
-2The milligram transition metal the time, will stop prepolymerization.When prepolymerization is to be suspended in when carrying out in the liquid medium, in inert gas, carry out drying back prepolymer and can the powdered isolated in form come out, drying temperature comprises between 50 and 80 ℃.By the prepolymer powder that solids are formed, its median size is between 50 and 300 microns, preferably between 70 and 250 microns.The size of this kind particle is to be applicable to vapour phase polymerization, particularly adopts the polymerization of fluidized-bed.
Vapour phase polymerization can for example carry out or be preferably in the fluidized-bed reactor carrying out in the reactor that stirs, in these reactors, polymer particle in forming process is to keep fluidized state by means of improving air-flow, and propulsive speed is 2 to 10 times of minimum fluidization velocity.Better being 5 to 8 times, in other words, generally is 15 to 80 cels, better is to be included between 40 to 60 cels.Upstream is comprising will carry out polymerization single polymerization monomer, also can select other components arbitrarily for use, for example hydrogen (chain-transfer agent) and/or rare gas element, for example methane, ethane, propane or nitrogen.The monomer material includes the diene that alpha-olefin maybe will carry out the polymeric alpha-olefines and select for use arbitrarily.Alpha-olefin maybe will carry out the polymeric alpha-olefines, has generally comprised 2 to twelve carbon atom.When it when the fluidized-bed, the alpha-olefin of some or want the polymeric alpha-olefines to contact further to carry out polymerization and make particle diameter expansion only with polymer particle.
The part alpha-olefines does not react and has just left fluidized-bed, before entering fluidized-bed reactor with compressor recirculation by cooling system to absorb the heat that it time is produced in reaction.
Mean pressure in the reactor can be near normal atmosphere, but in order to improve polymerization velocity, and pressure is more higher for well, for example can be between 0.5 and 5 kPa.
In reactor, keep temperature to certain level, satisfy polymerization and can carry out rapidly.In a word, not too near the softening temperature of polymkeric substance, form hot spot in the latter case and make the polymer melt gel preventing.General temperature is between 50 and 110 ℃, better is between 70 and 100 ℃.
Catalyst system will change prepolymer in advance into, in the continuous or semi-continuous then importing polymerization reactor.Taking out the polymkeric substance that is produced equally also can adopt the continuous or semicontinuous mode of known method to take out from reactor, especially can be with various mechanisms, device is to adorn an orifice plate at reactor bottom preferably, its effect is to cut off and be communicated with one to force down the chamber of pressing in keeping in reactor, when reaching given cycle, orifice plate is just opened, and the amount of the polymkeric substance that this just might will draw off hope enters that this is indoor, when orifice plate once closing again, polymerisate can be reclaimed from indoor.
Method of the present invention can make the polyolefins that obtains the low catalyst residual quantity, transistion metal compound and all low still not as the content of the organometallic compound of co-catalyst, and every gram polyolefine is preferably to contain and is less than 3 * 10
-4The transition metal of milligram-atom, best for being less than 2 * 10
-4The milligram-atom transition metal, this just might be very favourable and can satisfy the industrial production condition, produce the alpha-olefinic polymer of various different characters on a large scale, high density polyethylene(HDPE) (density is greater than 0.940) for example, Alathon and ethene are wherein arranged and have the multipolymer of the alpha-olefin of 3 to 12 carbon atoms, LLDPE (density is less than 0.940) contains ethene and one or more have the alpha-olefin copolymer of 3 to 12 carbon atoms, surpass 80% by the unit weight ethylene content, ethene, the elasticity ter-polymers of propylene and diene, the elastocopolymer of ethene and propylene, comprise between 30 and 70% by the unit weight ethylene content, the multipolymer of isotatic polypropylene and propylene and ethene and other alpha-olefins, surpass 90% by the unit weight propylene content, propylene and butene-1 copolymer are included between 10 and 40% by the 1-butylene content of unit weight.
Method of the present invention can accomplish to adopt quite a spot of co-catalyst, the polyolefine of production high yield under stable and reproducible vapour phase polymerization condition.These conditions are overcoming safety problem and being reduced in the presence of the hydrogen, and it is very favorable forming the alkane aspect owing to the hydrogenization of alpha-olefin.
Following example illustrates the present invention, but is not limited thereto:
Example 1
Preparation of catalysts:
Have stirring system and have in 1 liter of glass flask of heating, refrigerating unit, at one at N
2In 20 ℃, add 500 ml n-hexanes in turn under the atmospheric pressure, 8.8 gram magnesium powder and 1.2 gram iodine.Start and stir, reaction mixture is heated to 80 ℃, promptly adds 9.1 gram titanium tetrachlorides, 13.7 gram tetrapropyl titanic acid ester, added 74.5 with more than 4 hours at leisure then and restrain normal-butyl chlorination things, after adding, resulting reaction mixture is stirring and 80 ℃ of following maintenances 2 hours, cool to room temperature (20 ℃) then, the gained throw out washs three times with normal hexane, it is stand-by to obtain solid catalyst (A), to the analytical results of catalyzer (A), shows that the total titanium amount of every grammeatom contains:
0.9 the titanous of grammeatom
0.1 the titanic of grammeatom
3.7 the magnesium of grammeatom and
7.7 the chlorine of grammeatom
The composition of this catalyzer (A) is adapted to following general formula:
The preparation of performed polymer
Is in 5 liters of stainless steel reactors of 750 commentaries on classics agitators, in N at one with the per minute rotating speed
2Gas adds down 3 liters of normal hexanes, and is heated to 70 ℃, adds 14 milliliters one mole three-just-octyl group aluminium (TnOA) hexane solution with contain the catalyzer (A) that 14 milligram-atom titaniums prepare as stated above, its atomic ratio Al: Ti=1.0.TnOA is a kind of organo-aluminium compound, under vapour phase polymerization and copolymerization condition is liquid, the vapour pressure that is had in the time of 80 ℃ less than 0.13 handkerchief, closed reactor and add hydrogen then, until reactor pressure reaches 0.5 kPa, and feed ethene with the speed in 160 gram/times, common 3 hours, gained prepolymer (B) in rotating vaporizer in 70 ℃, N arranged
2Carry out drying under the air-flow, product is that every gram contains 0.029 milligram-atom titanium.
Co-polymerization in fluidized-bed
In a diameter was 45 centimetres fluidized-bed reactor, fluidization grid was equipped with in its bottom, and the speed of upstream is 45 cels, circulated and reaction gas mixture contains hydrogen, ethene, 1-butylene and nitrogen, its dividing potential drop following (PP) in 80 ℃:
Hydrogen dividing potential drop: 0.23 kPa
Ethylene partial pressure: 0.64 kPa
1-butylene dividing potential drop: 0.09 kPa
Nitrogen partial pressure: 0.66 kPa
Import in the reactor be 100 kilograms of inert anhydrous powder polyethylene as powder filler, added prepolymers (B) in per continuously then 210 seconds near 5 grams.
The inlet point place that is arranged in fluidized-bed reactor below the fluidization grid imports 0.05 mole of triethyl aluminum (TEA) solution that is dissolved in normal butane, normal feeding amount is per hour to be the TEA of 14 mmoles, TEA equals 455 handkerchiefs 80 ℃ vapour pressure, with under the vapour phase polymerization or copolymerization condition of alpha-olefin, basically be gasiform, the total amount of organo-aluminium compound is Al by atomic ratio in fluidized-bed: Ti equals 6.6.
At the working condition of ethene and butene-1 copolymer after stationary phase, about 25 kilograms of the copolymer powder of collect discharging subsequently/time, the amount that will remain on simultaneously in the fluidized-bed is 75 kilograms of these constant values, in this method, quite high productive rate is arranged, and per hour equaling, every cubic metre of fluidized-bed has 95 kilograms of multipolymers.Resulting copolymer powder has following characteristic:
-titaniferous amount: every gram is 1.00 * 10
-4The milligram-atom titanium
-melting index (MI
2.16): at 190 ℃, under 2.16 kilograms of loads, be measured as 5.8 grams/10 minutes.
-density (at 20 ℃): 0.937
Under these conditions, can find that also the ethane amount that forms is quite few, this reaction gas mixture contains the ethane of 4.5% volume.
It the results are shown in table 1
Example 2
Co-polymerization in fluidized-bed
In adopting the fluidized-bed reactor of example 1, upstream speed is 45 cels, circulates in 80 ℃, and the reaction gas mixture that contains includes hydrogen, ethene, 1-butylene and nitrogen, and (PP) is as follows for its dividing potential drop:
Hydrogen dividing potential drop: 0.20 kPa
Ethylene partial pressure: 0.56 kPa
1-butylene dividing potential drop: 0.08 kPa
Nitrogen partial pressure: 0.70 kPa
Import the interior 100 kilograms of inert anhydrous powder polyethylene of reactor as powder filler, add prepolymers (B) per continuously then 120 seconds near 5 grams.
Being positioned at inlet point place below the fluidization grid in fluidized-bed reactor imports and is dissolved in 0.05 mole of triethyl aluminum of normal butane (TEA) solution, normal feeding amount is per hour to be 12.5 moles TEA, the total amount of organo-aluminium compound in fluidized-bed, its atomic ratio is Al: Ti equals 3.8.
At the working condition of ethene and butene-1 copolymer after stationary phase, about 30 kilograms of the copolymer powder of collect discharging subsequently/time, the amount that will remain on simultaneously in the fluidized-bed is 75 kilograms of these constant values, on this method, quite high productive rate is arranged, per hour equaling every cubic metre fluidized-bed has 110 kilograms of multipolymers, and resulting copolymer powder has following characteristic:
-titaniferous amount: every gram is 1.46 * 10
-4The milligram-atom titanium
-melting index (MI
2.16): at 190 ℃, under 2.16 kilograms of loads, be measured as 5.7 grams/10 minutes.
-density (at 20 ℃): 0.938
Under these conditions, can find that also the ethane amount that forms is quite few, this reaction gas mixture contains the ethane of 4.0% volume.
It the results are shown in table 1
Example 3
Co-polymerization in fluidized-bed
In adopting the fluidized-bed reactor of example 1, upstream speed is 45 cels, circulates in 80 ℃, contains reaction gas mixture and includes hydrogen, ethene, 1-butylene and nitrogen, and (PP) is as follows for its dividing potential drop:
Hydrogen dividing potential drop: 0.17 kPa
Ethylene partial pressure: 0.48 kPa
1-butylene dividing potential drop: 0.07 kPa
Nitrogen partial pressure: 0.74 kPa
Import the interior 100 kilograms of inert water-free powder polyethylenes of reactor as powder filler, add prepolymers (B) per continuously then 155 seconds near 5 grams.
In fluidized-bed reactor, be positioned at the inlet point place below the fluidization grid, importing is dissolved in 0.05 mole of triethyl aluminum (TEA) solution of normal butane, normal feeding amount is per hour to be 6 moles TEA, the total amount of organo-aluminium compound in fluidized-bed, and its atomic ratio is Al: Ti equals 2.8.
At the working condition of ethene and butene-1 copolymer after stationary phase, about 20 kilograms of the copolymer powder of collect discharging subsequently/time, the amount that will remain on simultaneously in the fluidized-bed is 80 kilograms of these constant values, on this method, quite high productive rate is arranged, per hour equal that every cubic metre of fluidized-bed has 65 kilograms of multipolymers, resulting copolymer powder has following characteristic:
-titaniferous amount: every gram is 1.67 * 10
-4The milligram-atom titanium
-melting index (MI
2.16): at 190 ℃, under 2.16 kilograms of loads, be measured as 5.6 grams/10 minutes.
-density (at 20 ℃): 0.938
Under these conditions, can find that also the ethane amount that forms is quite few, this reaction gas mixture contains the ethane of 2.5% volume.
Example 4(comparative example)
Co-polymerization in fluidized-bed
Except the TEA with 42.2 mmoles per hour imported fluidized-bed reactor rather than the TEA with 14 mmoles per hour, by example 1 operation, like this, corresponding its atomic ratio of the total amount of organo-aluminium compound is Al in fluidized-bed: Ti equaled 18.0 entirely for all the other.
At the working condition of the multipolymer of ethene and 1-butylene after stationary phase, about 12 kilograms of the copolymer powder of collect discharging subsequently/time, the amount that will remain on simultaneously in the fluidized-bed is 72 kilograms of these constant values, on this method, quite low productive rate is arranged, per hour equal that every cubic metre of fluidized-bed has 45 kilograms of multipolymers, resulting copolymer powder has following characteristic:
The titaniferous amount: every gram is 2.07 * 10
-4The milligram-atom titanium
-melting index (MI
2.16): at 190 ℃, under 2.16 kilograms of loads, be measured as 6.8 grams/10 minutes.
-density (at 20 ℃): 0.939
Under these conditions, have quite a large amount of TEA to enter fluidized-bed, this just finds to generate a large amount of ethane, and promptly reaction gas mixture includes the ethane of 12.5% volume.It is disadvantageous for the volume productivity of multipolymer equally that a large amount of TEA imports fluidized-bed, and multipolymer has quite high titanium content equally.
The results are shown in table 1
Example 5(comparative example)
Co-polymerization in fluidized-bed
Except with 0.05 mole of TnOA solution, promptly per hour be that the speed of 14 mmoles imports fluidized-bed reactor to TnOA, rather than, promptly per hour be that the speed of 14 mmoles imports outside the fluidized-bed reactor that all the other are by example 1 operation with 0.05 mole of TEA solution.
Producing ethene and butene-1 copolymer after 48 hours, at reactor bottom, the following discovery of fluidization grid has liquid deposition, and the while is also observed the gathering of clinkering multipolymer and is deposited on the fluidization grid, so must stop copolymerization.
The results are shown in table 1
Example 6(comparative example)
The preparation of prepolymer
Import the reactor except the TnOA with 75.6 milligrams of moles replaces the TnOA of 14 mmoles, all the other are by example 1 operation, and the preparation employed catalyzer of prepolymer and its atomic ratio of co-catalyst amount are Al: Ti=5.4.
With the resulting prepolymer of this method (C), every gram contains 0.029 milligram-atom titanium.
Co-polymerization in fluidized-bed
Except adopt above-mentioned method prepare prepolymer (C) and per hour the TEA of 3 mmoles import fluidized-bed reactor rather than adopt prepolymer (B) and import the fluidized-bed reactor with the TEA of 14 mmoles per hour, all the other are by example 1 operation, the total amount of organo-aluminium compound in fluidized-bed, identical with example 1 by its atomic ratio, be Al promptly: Ti is 6.6.
Ethene and 1-butylene-dawn begin to produce with regard to the aggregation that the clinkering multipolymer is arranged and are deposited on the fluidization grid, cause to stop copolymerization
The results are shown in table 1
Example 7(comparative example)
Interpolymerization in fluidized-bed
Except importing the reactor with 14 mmole TEA rather than with 14 mmole TnOA, all the other are by the operation of example 1 method, are used for preparing the amount of the catalyzer and the co-catalyst of prepolymer, and the same with those conditions of example 1, its atomic ratio is that Al: Ti is 1.0.
To contain every gram be 0.029 milligram-atom titanium to resulting prepolymer (D) on this method.
Co-polymerization in fluidized-bed
Except above and prepolymer (D) preparation replaces the prepolymer (B), all the other are according to the method operation of example 2.
At the working condition of ethene and butene-1 copolymer after stationary phase, about 16 kilograms of the copolymer powder of collect discharging subsequently/time, the amount that will remain on simultaneously in the fluidized-bed is 78 kilograms of these constant values, in this method, per hour the productive rate of the multipolymer of every cubic metre of fluidized-bed is 55 kilograms, and resulting copolymer powder has following characteristic:
Titanium content: every gram is 5.00 * 10
-4The milligram-atom titanium
-melting index (MI
2.16): 2.6 grams/10 minutes
-density (at 20 ℃): 0.937
Under these conditions, prepolymer includes the volatile organo-aluminium compound of a great deal of, has found that its productive rate is quite little.The content of titanium is that high and melting index this multipolymer are quite low in the gained multipolymer, the results are shown in table 1
Example 8
Co-polymerization in fluidized-bed
In a diameter is 90 centimetres fluidized-bed reactor, fluidization grid is equipped with in its bottom, the gas velocity that rises is that 45 cels circulate, reaction gas mixture contains and is comprising hydrogen, ethene, 4-methyl-amylene (4MPI) and nitrogen, and (PP) is as follows for its dividing potential drop:
Hydrogen dividing potential drop: 0.05 kPa
Ethylene partial pressure: 0.32 kPa
4MPI dividing potential drop: 0.08 kPa
Nitrogen partial pressure: 1.15 kPas
Polymerization temperature is 80 ℃, and the temperature of recirculating gas is 63 ℃, and the dew point of recirculating gas is 48 ℃.
160 kilograms of ethene that has inertia, anhydrous powder by the operation of front preparation a kind of and 4MPI multipolymer are imported fluidized-bed as powder filler, and directly add fluidized-bed to 40 prepolymers (B) that restrain per then 125 seconds.
0.1 mole of triethyl aluminum (TEA) solution that is dissolved in normal hexane is introduced fluidized-bed reactor from fluidization grid lower inlet point, and normal feeding amount is per hour to be 6.6 mmole TEA.The total amount of the organo-aluminium compound in fluidized-bed, its atomic ratio is Al: Ti equals 3.
At the working condition of ethene and 4MPI multipolymer after stationary phase, collect subsequently about 160 kilograms of the copolymer powder of discharging/time, the amount that will remain on simultaneously in the fluidized-bed is 350 kilograms of these constant values, copolymer powder has following characteristic:
Titanium content: every gram is 2 * 10
-4The milligram-atom titanium
-melting index (MI
2.16): at 190 ℃, under 2.16 kilograms of loads, recorded 0.9 gram/10 minutes.
-density (at 20 ℃): 0.918
Example 9
Co-polymerization in fluidized-bed
Except being is three-just-octyl group aluminium that Al/Ti equals 1.5 to contain atomic ratio, rather than the prepolymer of triethyl aluminum imports outside the reactor, and all the other are operated according to example 8, and prepolymer D imports reactor with the speed of per 110 seconds 40 grams.
Reaction gas mixture includes hydrogen, ethene, 4MPI and nitrogen, has following dividing potential drop (PP):
Hydrogen dividing potential drop: 0.13 kPa
Ethylene partial pressure: 0.70 kPa
4MPI dividing potential drop: 0.175 kPa
Nitrogen partial pressure: 0.595 kPa
Polymerization temperature is that 80 ℃ and recirculating gas temperature are 71 ℃, and the dew point of recirculating gas is 70 ℃.
At the working condition of ethene and 4MPI multipolymer after stationary phase, collect subsequently about 100 kilograms of the copolymer powder of discharging/time, the amount that will remain on simultaneously in the fluidized-bed is 350 kilograms of these constant values, copolymer powder has following properties:
-titanium content: every gram is 3.7 * 10
-4The milligram-atom titanium
-melting index (MI
2.16): at 190 ℃, under 2.16 kilograms of loads, recorded 0.9 gram/10 minutes
-density (at 20 ℃): 0.918
Claims (10)
1, a kind of polymerization process of alpha-olefin, include the following step: (A) catalyzer of preparation prepolymer base, this step is the catalyst system that makes one or more alpha-olefin contact Ziegler-Natta types, this catalyst system is basically by halogen on the one hand, magnesium and belong to periodic table of elements IV, the catalyzer that the transition metal atoms of V or VI family is formed, be based on the co-catalyst that one or more belong to the organometallic compound of periodic table of elements II or III family metal on the other hand, (B) in the presence of the organo-metallic co-catalyst, prepolymer catalyst based under the vapour phase polymerization condition with the contacted method of one or more alpha-olefins, it is characterized by:
(1) co-catalyst that uses in step (A) is a kind of organometallic compound (a) of low volatility at least, the vapour pressure that is had in the time of 80 ℃ less than 65 handkerchiefs, its amount is the amount of the amount of metal in organometallic compound (a) to transition metal in catalyzer, by its atomic ratio be at least 0.5 and be at most 2.5 and
(2) co-catalyst that uses in step (B) is a kind of volatile organometallic compound (b) that has at least, the vapour pressure that is had is equal to or greater than 65 handkerchiefs in the time of 80 ℃, the amount of its amount metal in organometallic compound (b) is to the amount of transition metal in prepolymer is catalyst based, by its atomic ratio is 0.5 at least, and at organometallic compound (a) and (b) total amount of metal to the amount of transition metal in catalyzer, at least be 2.5 and be at most 9 that organometallic compound (b) is that the catalyzer with the prepolymer base imports polymerisation medium respectively by its atomic ratio.
2, according to a kind of method of claim 1, the vapour pressure of organometallic compound wherein (a) in the time of 80 ℃ is less than 40 handkerchiefs.
3, according to a kind of method of claim 1 or 2, the vapour pressure of organometallic compound wherein (b) is in the scope of 100 to 2,000 handkerchiefs (80 ℃).
4, according to a kind of method of top arbitrary claim, wherein organometallic compound (a) be a kind of be AlR with the general formula
nX
3The organo-aluminium compound of-n, wherein R is representing the alkyl that comprises from 4 to 20 carbon atoms, and X is hydrogen or halogen atom, or alcoholate base and n are from 1 to 3 any integer or mark.
5, a kind of method according to claim 1, wherein organometallic compound (b) is organic zinc compound or has general formula AlR ' nX
3The organo-aluminium compound of-n, wherein R ' is representing the alkyl that comprises from 1 to 3 carbon atom, and X is that hydrogen or halogen atom or alcoholate base and n are 1 to 3 any integer or marks.
6, according to a kind of method of claim 1, organometallic compound wherein (a) is to be selected from one or more three-just-butyl aluminium, three-just-hexyl aluminium, three-just-octyl group aluminium, diisobutyl alanate and diisobutyl aluminum muriate.
7, according to a kind of method of claim 1, organometallic compound wherein (b) is the triethyl aluminum that is selected from one or more, three-just-propyl group aluminium, diethyl aluminum muriate and ethyl aluminium sesqui chloride.
8, a kind of method according to claim 1, wherein prepolymer is catalyst based with one or more alpha-olefins and this catalyzer be that a kind of organometallic compound (a) contacts and makes at least, its amount is the amount that the amount of metal in organometallic compound (a) belongs to transition base in catalyzer, at least be 0.5 and be at most 2.5 by its atomic ratio, and every gram contains from 2 * 10
-3To 10
-1The milligram transition metal atoms.
9, a kind of method according to claim 1, wherein alpha-olefin carries out vapour phase polymerization in fluidized-bed, and pressure is included between 0.5 and 5 kPa, and temperature is included between 50 and 110 ℃.
10, a kind of polymerization process of alpha-olefin, include the following step: (A) preparation is catalyst based with prepolymer, this step is the catalyst system that makes one or more alpha-olefin contact Ziegler-Natta types, this catalyst system is basically by halogen on the one hand, magnesium and belong to periodic table of elements IV, the catalyzer that the transition metal atoms of V or VI family is formed, be based on the co-catalyst that one or more belong to the organometallic compound of periodic table of elements II or III family metal on the other hand, (B) in the presence of organo-metallic catalyst, prepolymer is catalyst based, under the vapour phase polymerization condition,, it is characterized by with the contacted method of one or more alpha-olefins:
(1) co-catalyst that in step (A), uses be at least a kind of be selected from contain three-just-butyl aluminium, three-just-hexyl aluminium, three-just-octyl group aluminium, diisobutyl alanate and the muriatic organometallic compound of diisobutyl aluminum and
(2) co-catalyst that uses in step (B) is a kind of organometallic compound that contains triethyl aluminum, three-just-propyl group aluminium, diethyl aluminum muriate and ethyl aluminium sesqui chloride that is selected from least.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8511999A FR2586022B1 (en) | 1985-08-06 | 1985-08-06 | POLYMERIZATION OF OLEFINS IN THE GASEOUS PHASE WITH A ZIEGLER-NATTA CATALYST AND TWO ORGANOMETALLIC COMPOUNDS |
| FR8511999 | 1985-08-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86105978A CN86105978A (en) | 1987-05-13 |
| CN1007353B true CN1007353B (en) | 1990-03-28 |
Family
ID=9322013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86105978A Expired CN1007353B (en) | 1985-08-06 | 1986-08-05 | Polymerization of olefins using a ziegler-natta catalyst and two organometallic compounds |
Country Status (18)
| Country | Link |
|---|---|
| US (1) | US4748221A (en) |
| EP (1) | EP0211624B1 (en) |
| JP (1) | JPH0725818B2 (en) |
| KR (1) | KR940004124B1 (en) |
| CN (1) | CN1007353B (en) |
| AT (1) | ATE53395T1 (en) |
| AU (1) | AU589986B2 (en) |
| BR (1) | BR8603716A (en) |
| CA (1) | CA1274343A (en) |
| DE (1) | DE3671749D1 (en) |
| ES (1) | ES2000598A6 (en) |
| FI (1) | FI85150C (en) |
| FR (1) | FR2586022B1 (en) |
| MY (1) | MY101271A (en) |
| NO (1) | NO167463C (en) |
| NZ (1) | NZ217040A (en) |
| PT (1) | PT83150B (en) |
| SG (1) | SG47892G (en) |
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| IT1281198B1 (en) | 1995-12-18 | 1998-02-17 | Montell Technology Company Bv | SHRINK FILMS BASED ON POLYOLEFIN COMPOSITIONS INCLUDING A LINEAR COPOLYMER OF ETHYLENE WITH ALPHA-OLEFINS |
| IT1292138B1 (en) * | 1997-06-12 | 1999-01-25 | Montell Technology Company Bv | EXTENSIBLE MULTILAYER FILM |
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| BE785673A (en) * | 1971-06-30 | 1973-01-02 | Naphtachimie Sa | POLYMERIZATION CATALYZERS OF OLEFINS PREPARED FROM DECOMPOSED ORGANOMAGNESIANS |
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-
1985
- 1985-08-06 FR FR8511999A patent/FR2586022B1/en not_active Expired
-
1986
- 1986-07-30 NZ NZ217040A patent/NZ217040A/en unknown
- 1986-07-31 DE DE8686305907T patent/DE3671749D1/en not_active Expired - Lifetime
- 1986-07-31 AT AT86305907T patent/ATE53395T1/en active
- 1986-07-31 EP EP86305907A patent/EP0211624B1/en not_active Expired - Lifetime
- 1986-08-04 AU AU60857/86A patent/AU589986B2/en not_active Ceased
- 1986-08-05 US US06/893,403 patent/US4748221A/en not_active Expired - Lifetime
- 1986-08-05 CN CN86105978A patent/CN1007353B/en not_active Expired
- 1986-08-05 PT PT83150A patent/PT83150B/en not_active IP Right Cessation
- 1986-08-05 NO NO863158A patent/NO167463C/en unknown
- 1986-08-05 BR BR8603716A patent/BR8603716A/en unknown
- 1986-08-06 JP JP61184994A patent/JPH0725818B2/en not_active Expired - Lifetime
- 1986-08-06 KR KR1019860006490A patent/KR940004124B1/en not_active Expired - Lifetime
- 1986-08-06 CA CA000515387A patent/CA1274343A/en not_active Expired - Lifetime
- 1986-08-06 FI FI863216A patent/FI85150C/en not_active IP Right Cessation
- 1986-08-06 ES ES8600909A patent/ES2000598A6/en not_active Expired
-
1987
- 1987-08-18 MY MYPI87001370A patent/MY101271A/en unknown
-
1992
- 1992-04-29 SG SG47892A patent/SG47892G/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| KR940004124B1 (en) | 1994-05-13 |
| FR2586022B1 (en) | 1987-11-13 |
| FR2586022A1 (en) | 1987-02-13 |
| PT83150B (en) | 1989-03-30 |
| MY101271A (en) | 1991-08-17 |
| KR870002167A (en) | 1987-03-30 |
| JPS6289706A (en) | 1987-04-24 |
| FI85150C (en) | 1992-03-10 |
| AU589986B2 (en) | 1989-10-26 |
| NO167463B (en) | 1991-07-29 |
| JPH0725818B2 (en) | 1995-03-22 |
| EP0211624A1 (en) | 1987-02-25 |
| FI863216L (en) | 1987-02-07 |
| EP0211624B1 (en) | 1990-06-06 |
| SG47892G (en) | 1992-06-12 |
| AU6085786A (en) | 1987-02-19 |
| ES2000598A6 (en) | 1988-03-01 |
| DE3671749D1 (en) | 1990-07-12 |
| BR8603716A (en) | 1987-03-10 |
| US4748221A (en) | 1988-05-31 |
| NO167463C (en) | 1991-11-06 |
| PT83150A (en) | 1986-09-01 |
| CA1274343A (en) | 1990-09-18 |
| FI85150B (en) | 1991-11-29 |
| CN86105978A (en) | 1987-05-13 |
| NO863158L (en) | 1987-02-09 |
| ATE53395T1 (en) | 1990-06-15 |
| NO863158D0 (en) | 1986-08-05 |
| FI863216A0 (en) | 1986-08-06 |
| NZ217040A (en) | 1989-09-27 |
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